Sodium Hydroxide → 4-Chloro-6-methyl-2-(methylthio)pyrimidine

HRID 2238640Notes

Reaction equation

HRID 2238640 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]([S:8][CH3:9])[N:3]=1.C[Li].Cl[C:13]1C(Cl)=C(O)C(C#N)=C(C#N)C=1O.[OH-].[Na+]>C(OCC)C.O1CCCC1.O>[Cl:1][C:2]1[CH:7]=[C:6]([CH3:13])[N:5]=[C:4]([S:8][CH3:9])[N:3]=1

Participants

8

Reactant 4

HCID 14798Sodium HydroxideHCID 971134-Chloro-2-methylthiopyrimidineHCID 2994934,5-Dichloro-3,6-dihydroxybenzene-1,2-dicarbonitrileHCID 178418348HCID 178418348, compound

Product 1

HCID 2411634-Chloro-6-methyl-2-(methylthio)pyrimidine

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

5.93 mL of 4-chloro-2-methylthiopyrimidine was dissolved in 50 mL of diethyl ether, and 100 mL of methyllithium (1M diethyl ether solution) was gradually added to the solution at −78° C. The reaction solution was stirred at 0° C. for 1 hour, and then a solution prepared by mixing 2.3 mL of water and 15 mL of tetrahydrofuran was added thereto. The reaction solution was stirred at the same temperature for 10 minutes, and then 50 mL of a tetrahydrofuran solution containing 13.7 g of 2,3-dichloro-5,6-dicyanohydroquinone was added thereto. The reaction solution was stirred at the same temperature for 1 hour, and then 100 mL of a 1 N aqueous solution of sodium hydroxide was added to the reaction solution. The obtained reaction solution was extracted with hexane, and the organic layer was washed with a 1 N aqueous solution of sodium hydroxide and saturated brine. After drying over anhydrous magnesium sulfate, the insolubles were filtered, and the filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 5.1 g of 4-chloro-6-methyl-2-(methylthio)pyrimidine [42-1] as a pale yellow solid.

Workup

  1. customa solution prepared
  2. additionwas added
  3. stirringThe reaction solution was stirred at the same temperature for 10 minutes
  4. additionwas added
  5. stirringThe reaction solution was stirred at the same temperature for 1 hour
  6. customThe obtained reaction solution
  7. extractionwas extracted with hexane
  8. washthe organic layer was washed with a 1 N aqueous solution of sodium hydroxide and saturated brine
  9. dry with materialAfter drying over anhydrous magnesium sulfate
  10. filtrationthe insolubles were filtered
  11. concentrationthe filtrate was concentrated under reduced pressure
  12. customThe obtained residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-39fce71304e840cbb295239ee7b72f8b
Source dataset
uspto-grants-2010_05
Patent number
US07718801B2

Reaction notes

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